Catalytic ammoxidation of propylene or isobutylene

ABSTRACT

An improved catalyst for the catalytic ammoxidation of propylene or isobutylene to acrylonitrile or methacrylonitrile, respectively, is provided. The catalyst has a composition corresponding to the empirical formula,

United States Patent [1 1 Umemura et al.

[451 Mar. 18, 1975 CATALYTIC AMMOXIDATION OF PROPYLENE OR ISOBUTYLENE[75] Inventors: Sumio Umemura; Kyoji Ohdan; Yasuo Bando, all of Ube;Mikio Hidaka, Shimonoseki; Kazuo Fukuda, Ube, all of Japan [73]Assignee: UBE Industries, Ltd.,

Ube, Yamaguchi-ken, Japan 22 Filed: July 13, 1973 211 Appl. No.: 378,978

[30] Foreign Application Priority Data UNITED STATES PATENTS 3,280,l67lO/l966 Schwarzer et al. 260/4653 3,641,100 2/1972 Yamada et a] 260/4653FOREIGN PATENTS OR APPLICATIONS 40-2532 2/1965 Japan 260/4653 1,024,4023/1966 United Kingdom 260/4653 Primary Examiner-Joseph P. Brust [57]ABSTRACT An improved catalyst for the catalytic ammoxidation ofpropylene or isobutylene to acrylonitrile or methacrylonitrile,respectively, is provided. The catalyst has a composition correspondingto the empirical formula,

where II is at least one metal of Group II of the Periodic Table; X isselected from Ti, Zr, Nb, Ta, V, Cr, Mn, Fe, Co and Ni; and a =0.3 10, b0.05 3.0, c 01 6.0 and d =0 5.0. The catalyst exhibits excellentconversion of the olefin and selectivity to the nitrile.

5 Claims, No Drawings CATALYTIC AMMOXIDATION OF PROPYLENE OR ISOBUTYLENEThis invention relates to a novel catalyst for ammoxidation of propyleneor isobutylene, and to a process for the manufacture of acrylonitrile ormethacrylonitrile wherein propylene or isobutylene, ammonia and oxygenare contacted in a vapor phase with the novel catalyst.

Various catalysts have been heretofore proposed for use in a vapor phasecatalytic ammoxidation of olefins to produce the correspondingunsaturated nitriles with a view to enhancing selectivity for a desiredunsaturated nitrile without reducing conversion of the olefin feed. Theknown ammoxidation catalysts include, in general, a combination ofoxides of two or more metals, for example, a MoBi-(P)oxide systemdescribed in Japanese Pat. No. 5870/1961, a Sn-Sb system described inJapanese Pat. No. 13966/1962, a USb sys- Fe-Sb system described inJapanese Pat. No l9l 1 H1963.

Generally, however, it has been difficult to obtain both highselectivity to desired unsaturated nitrile and high conversion ofolefin,i.e., there has been a need for controlling the conversion in order toobtain a high selectivity. With these known catalysts, yield ofunsaturated nitrile is at most approximately 70%. In general, since along contact time and a high temperature, e.g., approximately 450C ormore are required, the yield of unsaturated nitrile per weight ofcatalyst is inevitably reduced. and the life of the catalyst isshortened.

It is a main object of this invention to provide improved ammoxidationcatalyst and process which enable the manufacture of acrylonitrile ormethacrylonitrile at a relatively low reaction temperature for arelatively short contact time and with both high conversion and highselectivity.

Other objects and advantages will be apparent from the followingdescription including the working examples.

In accordance with this invention, there is provided a catalyst for theammoxidation of propylene or isobutylene to acrylonitrile ormethacrylonitrile, respectively, characterized by having a compositioncorresponding to the empirical formula,

wherein 11 is at least one metal selected from Groups 11 of the PeriodicTable; X is at least one metal selected from the group consisting oftitanium, zirconium, niobium. tantalum, vanadium, chromium, manganese,iron, cobalt and nickel; and each of a, b, c and d is a numberexpressing an atomic ratio of the respective metal to bismuth andfalling within the following ranges, a 0.3 to 10, b 0.05 to 3.0, c 0.1to 6,0 and d to 5.0, and e is a number which satisfies the averagevalency of the metals.

Further, there is provided a process for the manufacture ofacrylonitrile or methacrylonitrile from propylene or isobutylene whichcomprises contacting, in the vapor phase, at an elevated temperature amixture of propylene or isobutylene, ammonia and oxygen with a catalysthaving the particular composition as defined above.

Compared with the use of a conventional ammoxidation catalyst, theabove-defined catalyst, at a lower reaction temperature such asapproximately 400C, for a shorter contact time, produces an unexpectedlygood yield of or more, considering the above process conditions. a

The catalyst of this invention is characterized by haw ing thecomposition corresponding to the empirical formula,

In this empirical formula, II signifies at least one metal selected fromGroup II of the Periodic Table. The metal 11 preferably includes,calcium, barium, zinc, cadmium, strontium, magnesium and mercury. Ofthese, calcium, barium and zinc are most preferable. X signifies atleast one metal selected from, titanium, zirconium, niobium, tantalum,vanadium, chromium, manganese, iron, cobalt and nickel.

Atomic ratios of the respective metals to bismuth, which are indicatedby a, b, c and din the empirical formula are as follows,

a 0.3 10, preferably 05 3.0

b 0.05 3.0, preferably 0.1 -l.5

c 0.1 6.0, preferably 0.2 5.0

1! =0 5.0, preferably 0.1 4.0

e is a number taken to satisfy the average valency of the metalsemployed, and in general falls within the range from 3.2 to 61.5.

In the case where the catalyst contains chromium in an amount such thatan atomic ratio of chromium to bismuth is within the range of 0.1 to3.0, the catalyst exhibits excellent dimensional stability andmechanical properties, as compared with a catalyst containing no chrome,and especially a conventional catalyst.

These metal ingredients may be present in the catalyst compositioneither as a mixture ofthe metal oxides or in a bonded state.

Typical procedures for the manufacture of some of the catalysts will beillustrated.

A stated amount of ammonium paratungstate is dissolved in hot water. Astated amount of calcium nitrate is dissolved in the aqueous solution.Successively, a solution of a stated amount of bismuth nitrate in nitricacid and a solution of a stated amount of ammonium molybdate in aqueousammonia are added by drops into the above solution at the same time,while the solu tion is stirred, thereby forming a precipitate. Afterleaving overnight, the precipitate is washed by repeated the cantation,filtered, dried and finally, calcined. The calcined product ispulverized and shaped into pellets or particles of desired shape andsize. Similarly, catalysts which contain barium, zinc or other metals ofGroup II of the Periodic Table, substituted for the calcium, may also beprepared.

Bi-Mo-W-llX-O catalyst (1) A stated amount of ammonium paratungstate isdissolved in hot water, followed by the addition of niobium pentaoxide.In this solution, a stated amount of calcium nitrate is dissolved, andsuccessively, a solution of a stated amount of bismuth nitrate in nitricacid and a solution of a stated amount of ammonium molybdate in aqueousammonia are added by drops thereinto at the same time, while thesolution is stirred, thereby forming a precipitate. The precipitate istreated in a manner similar to that described in the previous example.Other catalysts, which contain barium, zinc or other Group II metalssubstituted for the calcium, and

other metals classified as X, substituted for the niobium, may also beprepared by a similar procedure.

BiMoWll-XO catalyst (2) A solution of ammonium molybdate in aqueousammonia is treated with a solution of calcium nitrate in nitric acid,the amounts of Mo and Ca being equimolar, to produce a coprecipitate.The coprecipitate is washed, filtered, dried and then, calcined. Theproduct is calcium molybdate expressed by the formula Ca- MoO A solutionof iron nitrate in nitric acid is treated with a solution of bismuthnitrate in nitric acid, the amounts of Fe and Bi being equimolar. Themixed solution is heated to dryness until generation of nitrogen oxideceases. The obtained solid is calcined to form bismuth ferrate,expressed by the formula BiFeO The calcium molybdate (CaMoO and thebismuth ferrate (BiFeO are kneaded with water, dried, calcined and then,shaped into pellets or particulate forms.

Similarly, other catalysts may be prepared by mixing and kneading, forexample, calcium molybdate (Ca- M with bismuth vanadate (BiVO,), bismuthtitanate (Bi- Ti O bismuth tantalate (BiTaO bismuth tungstate (Bi O .WOBi O .3WO 3Bi O .4WO bismuth niobate (Bi NbO BiNbO and bismuth zirconateThe procedures for the preparation of the catalyst are not critical. Thecatalyst may be prepared by procedures other than those illustratedabove. Also, raw materials used for the preparation of the catalyst arenot critical.

The catalyst may be used alone or in combination with any of the knowncarriers. As carriers, those which bring favorable effects for thereaction involved, such as silica, alumina, alumina-silica, silicate,diatomaceous earth and the like which have been deactivated by, e.g.,heat-treatment, may suitably be employed. These carriers may be used forexample from 10 to 90% by weight of the catalyst.

The catalyst may be employed in either a fluidized bed or a fixed bed.although it is more advantageously used in a fixed bed since the life ofthe catalyst is extremely long.

Size and configuration of the catalyst grain are not critical but dependprimarily on whether the catalyst is used in a fluidized bed or fixedbed. The catalyst may also be shaped or grained by suitable knownmethods in order to provide required mechanical strength.

Propylene or isobutylene feed used in the process of the invention isnot necessarily highly purified, but a mixture of propylene orisobutylene with saturated hydrocarbons such as propane and butane mayalso be used. However, any gas substantially inluencing the ammoxidationreaction to any appreciable degree under the particular reactionconditions, for example, acetylene, n-butylene and the like, shouldpreferably be excluded from the feed for the reaction since they mayform undesirable by-products.

Likewise, other diluents which do not influence the ammoxidationreactionn, may be present in the reaction mixture without deleteriouseffect. Such diluents include, for example, steam. nitrogen and carbondioxide. The amount of diluent in the feed for the reaction ispreferably more than 0.5 moles per mole of propyally preferred to add atleast 0.5 moles of steam to the feed per mole of propylene orisobutylene.

As a source of oxygen which is used in the ammoxidation reaction of theinvention, pure oxygen and any oxygen containing gas may be used.Particularly, air may be advantageously used. A relative proportion ofoxygen in the feed for the reaction is suitably from 0.8 to 4 moles, andpreferably from. about 1.0 to about 2.5 moles per mole of propylene orisobutylene. Feeding of oxygen is excess of the above limit inevitablyleads to formation of by-products such as carbon monoxide and carbondioxide. On the contrary, feeding of oxygen less than the above rangebrings about a reduction of seleclene or isobutylene. Steam in thereaction mixture notv I only acts as a diluent but also exhibits effectsto entivity of the end product.

A relative proportion of ammonia in the feed for the reaction mixture issuitably from 0.5 to 3 moles, and preferably from about 0.8 to 1.2 molesper mole of propylene or isobutylene.

The ammoxidation reaction is usually carried out under atmosphericpressure although slightly superatmospheric or slightly reducedpressures may be used if desired.

The reaction is suitably carried out at a temperature ranging between300C and 550C, preferably between 350C and 500C. Reaction temperaturesexceeding the upper limit cause the decomposition of propylene orisobutylene, the reduction of selectivity and the promotion ofside-reactions. It is worthy of special mention that the ammoxidationreaction is advantageously performed at approximately 400C.

A contact time of 0.3 to 20 seconds, especially 0.5 to 15 seconds ispreferred. A contact time exceeding the upper limit causes thedecomposition of the reaction product and other undesirableside-reactions.

The following examples are given to illustrate the invention and are notto be considered as limiting in any sense. ln the examples, 7cconversion" and selectivity" are defined as follows:

% conversion (moles of propylene or isobutylene consumed)/(moles ofpropylene or isobutylene supplied) X selectivity (moles of propylene orisobutylene converted to acrylonitrile or methacrylonitrile)/- (moles ofpropylene or isobutylene consumed) X 100 and is by weight.

EXAMPLES l 6 BiMo-WCa catalyst (1) 90.6 g. of ammonium paratungstate[(NH W O .5H O] and 245.6 g of calcium nitrate [Ca(NO .4H O] weredissolved in l l of water maintained at 60C, while being stirred. Tothis solution, were added, by drops at the same time, a solution of168.2 g bismuth nitrate [Bi(NO .5H O] in 202 ml of a 10% nitric acid anda solution of 122.6 g ammonium molybdate [(NH ),;MO O .4H O] in 267 mlof a 10% aqueous ammonia. Successively, a lO /c aqueous ammonia wasadded to the reaction mixture thereby adjusting the pH to 4.0 to form aprecipitate. After leaving overnight. the precipitate was washed by fordecantations, filtered and dried. The product was shaped into tabletshaving a diameter of 5 mm, and then calcined at 600C for 16 hours toprepare a catalyst.

Using the catalyst so prepared. ammoxidation reaction was performed bythe following procedures.

111 Example 1, ml of the catalyst, so prepared, was packed into aU-shaped glass reaction tube having an inner diameter of 10 mm. Agaseous mixture of propylene, ammonia, air and steam, the molar ratio ofthe four components being 27 :27: 300: 106, respectively, was passedthrough the catalyst-packed reaction tube maintained at 420C at a flowrate of 460 ml/min. The contact time was 2.6 seconds.

In Example 2, the procedure of Example 1 was followed wherein the amountof the catalyst packed into the reaction tube was ml, the reactiontemperature was 400C and the contact time was 3.9 seconds, with allother conditions remaining substantially the same.

In Example 3, the procedure of Example lwas followed wherein isobutylenewas used in substitution for propylene with all other conditionsremaining substantially the same.

In Examples 4, 5 and 6, the procedure of Example 1 was followed whereincatalysts containing the four metal ingredients in varied atomic ratioswere employed with all other conditions remaining substantially thesame.

at 60C, while being stirred. To this solution. were added by drops atthe same time, a solution of 168.2 g bismuth nitrate lBi(NO -,);;.5H OIin 202 ml of a 10% nitric acid and a solution of 1 12.6 g ammoniummolybdate [(NH Mo O .4H O] in 267 ml of 10% aqueous ammonia.Successively, 10% aqueous ammonia was added to the reaction mixturethereby adjusting the pH to 4.0 to. form a precipitate. After leavingovernight. the precipitate was washed by four decantations, filtered anddried. The dried product was shaped into tab lets and then calcined at600C for 16 hours to prepare a catalyst.

Using the catalyst so prepared, ammoxidation reaction of propylene wasperformed by the same procedure as that of Example 1. The results areshown in Table 11,

EXAMPLE 9 Bi-Mo-WZn catalyst The procedure for the preparation ofcatalyst in Example 8 was repeated wherein 153.5 g of zinc nitrate]Zn(NO .6H O] were used in substitution for the 146 g of barium nitratewith all other conditions remaining The results are shown in Table l.substantially the same. whereby a catalyst consisting of Table 1 Exam(onstrict" ple Fccd- Atomic version tivity No. stock Product Catalystratio (K1 7!) l Pro- AN *1 Bi-Mo-W-Ca 1:2:1:3 96.0 89.1

pylene.

2 do. do. do. do. 94.6 88.9

150- 3 butyl- MAN *2 do. do. 97.3 83.2

ene 4 Pro- AN do. 1:2: 1:6 963 86.6

pylene 5 do. do. do. 2:l:2:4 89.3 88.2 6 do. do. do. 1:2:l:1 91.2 85.3

Note: *1 AN: Acrylonitrile *2 MAN: Methacrylonitrile EXAMPLE 7molybdenumlbismuth, tungsten, zinc and oxygen was prepared.

BiMo-W-Ca catalyst (2) 90.6 g of ammonium parantungstate [(NH ,W O ,.5HO] and 122.8 g of calcium nitrate [Ca(NO .4H O] were dissolved in 1lofhot water. To the solution, were added 168.2 g of bismuth nitrate[Bi(NO .5H O] and 112.6 g of ammonium molybdate [(NH Mo O .4H O] at thesame time while the solution was vigorously stirred. The slurry soobtained was heated to dryness in a sand batn until generation of N0 gasceased. To the product was added 1.5% of graphite. Then, the mixture wasshaped into tablets having a diameter of 5 mm. The tablets were calcinedat 600C for 10 hours to prepare a catalyst.

Using the catalyst, ammoxidation reaction of propylene was performed bythe same procedure as that of Example 1. The results are shown in TableI1.

EXAMPLE 8 BiMo-WBa catalyst 90.6 g of ammonium paratungstate I(NH,) ,W O,.SH O] and 146 g of barium nitrate lBa(NO;;) were dissolved in 1 1 ofwater maintained Using the catalyst so prepared, ammoxidation reactionof propylene was performed by the same procedure as that of Example 1.The results are shown in Table II.

Comparative Example 1 Bi-Mo-Ca catalyst 245.6 g ofcalcium nitrate [Ca(NO.4H O] was dissolved in l l of water maintained at 60C. To thissolution, were added by drops at the same time a solution of 168.2 gbismuth nitrate [Bi(NO .5H O] in 202 m1 of a 10% nitric acid and asolution of 122.6 g ammonium molybdate [(NH Mo O .4H O] in 267 m1 of a10% aqueous ammonia. Then, an aqueous ammonia was added to the reactionmixture thereby adjusting the pH to 4.0 to form a precipitate. Theprecipitate so formed was treated in the same manner as that of Examplel to prepare a catalyst.

Using the catalyst so prepared, ammoxidation reaction of propylene wasperformed by'the same procedure as that of Example 1. The results areshown in Table II.

Comparative Example 2 Example 11 Example 12 Amount of catalyst 30 ml 10ml Reaction temperature 400C 450C Contact time 3.9 see l.3 sec InExample 13, ammoxidation reaction of isobutylene was performed by thesame procedure as that of Example 10 except that isobutylenewas employedin substitution for propylene.

In Examples l4, l5 and 16, the procedure of Exam- Ta'B'Ie II ExampleFeedstock Prd- Catalyst Atomic Con- Selec- No. uct ratio version tivity7 Propylene AN Bi-Mo-W-Ca 1:2: 1 l .5 93.5 87.] 8 do. do. Bi-Mo-W-Ba do.97.2 85.3 9 do. do. Bi-Mo-W-Zn do. 97.2 85.3 Comparado. do. Bi-Mo-Ca12:15 70.3 I 73.8 live 1 Com- 1 parado. do. Bi-Mo-W 4:l:2 85.6 75.6 tive2 EXAMPLES 10- 16 w ple 10 was followed wherein catalysts containing theCatalyst (1) filve nlletaliplgridiefits in vadr te d atomic ratiostil/ere em- 74.1 g of ammonium paratungstate p oye W1 a 0 er con 1 ionsremaining t e same.

[(NHU W O SH O]. 9.4 g of niobium pentaoxide [Nb O ]and 251.3 g ofcalcium nitrate [Ca(NO .4- H O] were dissolved in 11 of water maintainedat 60C, while being stirred. To this solution, were added by drops atthe same time a solution of 172.2 g bismuth nitrate [Bi(NO .5H O] in 207ml of a nitric acid and a solution of 125.5 g ammonium molybdate[(NH4)(,-MO7024-4H2O] in 298 ml ofa 10% aqueous ammonia. successively, a10% aqueous ammonia was added to the reaction mixture thereby adjustingthe pH to 4.0 to form a precipitate. The precipitate was treated in thesame manner as that of Example 1 to prepare a catalyst.

ln Example 10, using the catalyst so prepared. ammoxidation reaction ofpropylene was performed by the same procedure as that of Example 1.

In Examples 11 and 12, the procedure of Example 10 was followed whereinthe process conditions were varied as follows with all other conditionsremaining substantially the same.

The results of Examples 10 16 are shown in Table III.

EXAMPLE 17 BiMo-WCa-Nb catalyst 2 i 74.1 g of ammonium paratungstate[(NH ,W O .5H O], 9.4 g of niobium pentaoxide [Nb O and 125.7 g ofcalcium nitrate [Ca(NO .4- H O] were dissolved in 1 l of hot water. Tothe solution, were added 172.2 g of bismuth nitrate [Bl(NO3) .5' H 0]and 125.5 g of ammonium molybdate ](NH Mo O .4H O] at the same timewhile being vigorously stirred. The slurry so obtained was heated todryness in a sand bath until generation of N0 gas ceased. From thisdried product, a tabletted catalyst was prepared in the same manner asthat of Example Using the catalyst so prepared, ammoxidation reaction ofpropylene was performed by the same procedure as that of Example 10. Theresults are shown in Table III.

Table III Example Feedstock Prod- Catalyst Atomic C on- Selec- No. uctratio version tivity 0 10 Propylene AN Bi-Mo-W-Ca-Nb 1:210:21: 96.590.0,

3:012 11 do. do. do. do. 95.0 89.8 l2 do. do. do. do. 94.0 88.5 13[sobutylene MAN do. do. 980 84.3 14 Propylene AN do. l:2:0.5:

3:0.5 96.3 89.6 15 do. do. do. 1:l.8:0.3

16:07 95.5 87.5 16 do. do. do. l:l.8:0.9

:6:0.l 96.5 88.5 17 do. do. do. l:2:0.8:

BiMo-W-Ca-Ti catalyst (11 75.1 g of ammonium paratungstate [(NH W O .5HO], 5.75 g of titanium dioxide [TiO and 254.5 g of calcium nitrate[Ca(NO 4H O] were dissolved in 1 l of water maintained at 60C whilebeing stirred. To this solution, were added by drops at the same time asolution of 174.4 g bismuth nitrate [Bi(NO .5H O] in 210 ml of a 10%nitric acid and a solution of ammonium molybdate [(NH Mo O .4- H O] in301 ml. of a 10% aqueous ammonia. Successively, a 10% aqueous ammmoniawas added to the reaction mixture thereby adjusting the pH to 4.0 toform a precipitate. The precipitate was treated in the same manner asthat of Example 1 to prepare a catalyst.

1n Example 18, using the catalyst so prepared, ammoxidation reaction ofpropylene was performed by the same procedure as that of Example 1.

ln Examples 19 and 20, the procedure ofExample 18 was followed whereinthe process conditions were varied as follows with all other conditionsremaining substantially the same.

. Example 19 Example 20 Amount ofcatalyst ml 10 ml Reaction temperature400C 450C Contact time 3.9 sec 1.3 sec EXAMPLE 25 Bi--Mo-WCa-'l'icatalyst (2) A catalyst was prepared from the following compounds by thesame procedure as that of Example 17.

Ammonium paratungstate [(NH W O '5H O] 75.1 g Titanium dioxide [TiO 5.75g Calcium nitrate [Ca(NO,-,) '4H O] 127.3 g Bismuth nitrate[Bi(NO,,);,'5H O] 174.4 g Ammonium molybdate [(NH. ;Mo O- ,,-4H O] 127.1g

Using the catalyst so prepared, ammoxidation reaction of propylene wasperformed by the same procedure as that ofExample 10 with all otherconditions remaining substantially the same. The results are shown inTable IV.

ExKMPLEs EL i9 Bi-Mo-W-Ca-Ta catalyst 72.6 g of ammonium paratungstate[(NH W O ,.5H O], 15.4 g of tantalum pentaoxide [Ta O and 246.2 g ofcalcium nitrate [Ca(NO .4- H O] were dissolved in l l of watermaintained at 60C, while being stirred. To the solution, were added bydrops at the same time a solution of 168.7 g bismuth nitrate [Bi(NO .5HO] in 203 ml of a 10% nitric acid and a solution of 122.9 g ammoniummolybdate [(NH ),,MO O .4H O] in 291 ml ofa 10% aqueous ammonia. Then, a10% aqueous ammonia was added to the reaction mixture thereby adjustingthe pH to 4.0 to form a precipitate. The precipitate was treated in thesame manner as that of Example 1 to prepare a catalyst.

1n Examples 26 and 27, using the catalyst soprepared, ammoxidationreactions ofpropylene and isobutylene, respectively, were performed bythe same pro cedure as that of Example 1.

In Examples 28 and 29, the procedure of Example 26 was followed whereincatalysts containing the five metal ingredients in varied atomic ratioswere employed, with all other conditions remaining the same. The resultsof Examples 26 29 are shown in Table IV.

EXAMPLES 30 33 BiMoWCa-Zr catalyst 74.3 of ammonium paratungstate [(NH WO .5H O], 19.0 g of zirconium nitrate [ZrO(NO .2H O] and 251.9 g ofcalcium nitrate [Ca(NO .4H O] were dissolved in l l of water maintainedat 60C, while being stirred. To this solution, were added by drops atthe same time a solution of 172.6 g bismuth nitrate [Bi(NO;,) .5H O] in207 ml of a 10% nitric acid and a solution of 125.8 g ammonium molybdate[(Nl-l..) Mo;O .,.4H Ol in a 10% aqueous ammonia. Successively, a 10%aqueous ammonia was added thereby adjusting the pH to 4.0 to form aprccip' itate. The precipitate was treated in the same manner as that ofExample 1 to prepare a catalyst.

In Examples 30 and 31, using the catalyst so prepared, ammoxidationreactions of propylene and isobutylene, respectively, were performed bythe same procedure as that of Example 1.

In Examples 32 and 33, the procedure ofExample 30 was followed whereincatalysts containing the five metal ingredients in varied atomic ratioswere employed, with all other conditions remaining substantially thesame. The results of Examples 30 33 are shown in Table IV.

11 12 Table IV Continued Exam- Catalyst Atomic C on- Selecple FeedstockProdratio vertivity No. uct sion (70) 22 f Propylene AN do. 122:0.5:

310.5 95.7 89.1 23 do. do. do. 1:l.8:0.3

1610.7 95.0 86.8 24 do. do. do. l:l.8:0.9

:6:0.1 95.9 88.1 25 do. do. do. l:2:0.8:

l.5:0.2 93.5 89.0 26 do. do. Bi-Mo-W-Ca-Ti l:2:O.8:3 :0.2 95.7 88.3 27Isobutylene MAN do. do. 97.0 82.0 28 Propylene AN do. l:2:O.5:

3:0.5 95.4 87.9 29 do. do. do. 1:1.8:0.9

:6:0.1 95.6 87.0 30 do. do. Bi-Mo-W-Ca-Zr 12210.8:

3:0.2 95.5 87.5 31 150- butyl- MAN do. do. 97.0 82.2 ene 32 Propylene ANdo. l:2:0.5:

3:0.5 95.3 87.0 33 do. do. do. 1:18:09

EXA P S 34 solution, were added at the same time 184.4 g of his-Catalyst (1) muth nitrate [Bl(NO .5H- O] and 134.4 g of ammog ofammonium paratungstate nium molybdate [(Nl-l Mo O .4H O] while belng[(NHQ W O SH- O], 29.0 g'of ferric nitrate [Fe(- NO .9H O] and 254.5 gof calcium nitrate [Ca(- NO .4H O] were dissolved in l 1 of watermaintained at 60C, while being stirred. To this solution, were added bydrops at the same time a solution of 174.4 g bismuth nitrate [Bi(NO .5HO] in 210 ml ofa nitric acid and a solution of 127.0 g ammoniummolybdate in 302 ml of a 10% aqueous ammonia. Then, a 10% aqueousammonia was added thereby adjusting the pH to 4.0 to form a precipitate.The precipitate was treated in the same manner as that of Example 1 toprepare a catalyst.

ln Examples 34 and 37, using the catalyst so prepared. am moxidationreactions of propylene and isobutylene. respectively, were performed bythe same procedure as that of Example 1.

ln Examples 35 and 36, the procedure ofExample 10 was followed whereinthe process conditions were varied as follows, with all other conditionsremaining substantially the same.

Example 35 Example 36 Amount of catalyst ml 10 ml Reaction temperature400C 450C Contact time 3.9 sec 1.3 see EXAMPLE 41 BiMo-WCa-Fe catalyst(2) 49.6 of ammonium paratungstate [(NH W O .5H O], 76.8 g of ferricnitrate [Fe(- NO .9H O] and 269.2 g of calcium nitrate [Ca(- NO .4H O]were dissolved in 1 l of hot water. To this vigorously stirred. Theslurry so obtained was heated to dryness in a sand bath until generationof N0 gas ceased. 1.5% of graphite was added to the dried product. Then,the mixture was shaped into tablets having diameter of 5 mm. The tabletswere calcined at 600C for 10 hours to prepare a catalyst.

Using the catalyst so prepared, ammoxidation reaction of propylene wasperformed by the same procedure as that of Example 34. The results areshown in Table V.

EXAMPLES 42 45 BiMoWCa-Co catalyst 49.8 g of ammonium paratungstate[(NH4)1 W1gO4 -5H20]. g Of CObalt nitrate {CO(- NO .6H- .O] and 270.1 gof calcium nitrate [Ca(- NO;,) .4H- .O] were dissolved in l l of watermaintained at 60C. To this solution, were added by drops at the sametime a solution of 185.0 g bismuth nitrate [Bit- NO );,.5H O] in222m1ofa 10% nitric acid and a solu tion of 134.8 g ammonium molybdate[(NH Mo O .4H O] in 320 ml ofa 10% aqueous ammonia. Successively, a 10%aqueous ammonia was added thereby adjusting the pH to 4.0 to form aprecipitate. The precipitate was treated in the same manner as that ofExample 1 to prepare a catalyst.

In Example 42, using the catalyst so prepared, ammoxidation reaction ofpropylene was performed by the same procedure as that of Example 1.

ln Examples 43, 44 and 45, the procedure of Example 42 was followedwherein catalysts containing the five metal ingredients at varied atomicratios were employed with all other conditions remaining substantiallythe same.

The results of Examples 42 45 are shown in Table V.

EXAMPLES 46 49 Bi- MoWCa-N i catalyst 49.8 of ammonium paratungstate[(NH ,W O .5H O], 270.1 g of calcium nitrate [Ca(NO .4l-l O] and 55.5 gof nickel nitrate {Ni(- NO .6H O] were dissolved into 1 l of watermaintained at 60C, while being stirred. To this solution, there weredropped at the same time a solution of 185.1 g bismuth nitrate [Bi(NO.5H O] in 222 m1 of a nitric acid and a solution of 134.9 g ammoniummolybdate [(NH4)GMO7O24.4H2O] in 320 ml ofa 10% aqueous ammonia.Successively. a 10% aqueous ammonia was added thereby adjusting the pHto 4.0 to form a precipitate. The precipitate was treated in the samemanner as that of Example 1 to prepare a catalyst.

In Example 46, using the catalyst so prepared, ammoxidation reaction ofpropylene was performed by the same procedure as that of Example 1.

In Examples 47 49, the procedure of Example 46 was followed whereincatalysts containing the five metal ingredients at varied atomic ratioswere employed with all other conditions remaining substantially thesame.

The results of Examples 46 49 are shown in Table V.

EXAMPLES 50 53 BiMo-W-CaCr catalyst 49.8 g of ammonium paratungstate[(NH,) ,,W O .5H O]. 76.3 g of chromium nitrate [Cr(NO .9H O] and 269.9g of calcium nitrate [Ca(NO .41-1 O] were dissolved in l lof watermaintained at 60C, while being stirred. To this solution. were added bydrops at the same time a solution of 184.9 g bismuth nitrate [Bi(NO .5HO] in 222 ml of a 10% nitric acid and a solution of 134.7 g ammo niummolybdate [(NH Mo O .4H O] in 319 ml ofa 10% aqueous ammonia.successively, a 10% aqueous ammonia was added thereby adjusting the pHto 4.0 to form a precipitate. The precipitate was treated in the samemanner as that of Example 1 to prepare a cata- EXAMPLES 54 57 49.9 g ofammonium paratungstate [(NH ,W O .5l-l 90.0 g of manganese nitrate[Mn(NO .6H O] and 270.8 g of calcium nitrate [Ca(- NO .4H O] weredissolved in l l of water maintained at 60C, while being stirred. Tothis solution, were added by drops at the same time a solution of 185.5g bismuth nitrate [Bi(NO .5H- O] in 223 ml of a 10% nitric acid and asolution of 135.2 g ammonium molybdate [(NH MO O .4H O] in 321 ml ofa10% aque- 35 ous ammonia. successively, a 10% aqueous ammonia was addedthereby adjusting the pH to 4.0 to form a precipitate. The precipitatewas treated in the same manner as that of Example 1 to prepare acatalyst.

1n Example 54, using the catalyst so prepared. am-

moxidation reaction of propylene was performed by the same procedure asthat of Example 1.

1n Examples 55, 56 and 57, the procedure of Example 54 was followedwherein catalysts containing the five metal ingredients at varied atomicratios were employed with all other conditions remaining substantiallythe same.

The results of Examples 54 57 are shown in Table lyst. V.

Table V Exam- Conple Feedstock Prod- Catalyst Atomic ver- Selec- No. uctratio sion tivity 19 1) 34 Propylene AN Bi-Mo-W-(a-Fe 112:0.8: 98.7119.0

310.2 35 do. do. do. do. 96.6 88.6 36 do. do. do. do. 95.2 87.6 37Isobutylcne MAN do. do. 99.0 81.6 38 Propylene AN do. 111.5105

13:02 97.4 87.0 39 do. do. do. l:l.8:0.3

1610. 98.8 86.3 40 do. do. do. 1:111:61

0.3 94.2 88.1 41 do. do. do. 12210.51

320.5 96.9 85.6 42 do. do. Bi'Mo-W-Ca-Co l:2:0.5:

310.5 98.6 85.0 43 do. do. do. 111.5:0.5.

3:0.3 97.8 88.0 44 do. do. do. 1:2:113:

0.2 97.6 88.5 45 do. do. do. 1:2:116:

0.5 99.0 86.2 46 do. do. Bi-Mo-WCa-Ni 320.5 47 do. do. do. 1:l.5:0.290.1 87.7

610.2 48 Propylene AN Bi-Mo-W-Ca'Ni 111.8:114. 91.7 87.6

1 49 do. do. do. l:2.0:0.8.

3:08 979 85.5 50 do. do. Bi-Mo-W-Ca-Cr 1:2:0.5.3.

16 Table V Continued lixnm- Conplc Feedstock Prod- Catalyst Atomic ver-Selcc- No. uct ratio sion tivity 5| do. do. do. 12120.5:2: 96.7 86.7

0.8 52 do. do. do. 11220.2.3. 90.9 88.2

1.0 53 do. do. do. 1:3:1.0: 92.3 84.9

610.2 54 do. do. Bi-Mo-W-Ca-Mn 12210.5:3: 94.3 89.2

0.8 55 dov do. do. l:O.5:1.0: 92.2 87.4

3:05 56 do. do. do. l:l:0.5:3: 94.4 88.6

0.2 57 do. do. do. 11320.8 93.1 87.8

mesh (Tyler standard sieve), which was employed as a catalyst.

4 ml of the catalyst was packed into a U-shaped stainless steel reactiontube having an inner diameter of 8 mm. A gaseous mixture of olefin(propylene in Examples 58 and 60 and (isobutylene in Examples 59 and61), ammonia, steam and air, a molar ratio of the four components being1 l 2 7.5, respectively. was passed through the catalyst packed reactiontube maintained at 420C at a flow rate of 80.5 ml/min. The contact timewas 3 seconds. The results are shown in Table V1.

' Table 7 7 w Exam- Conple Feedstock Prod- Catalyst Atomic ver- Selec-No. uct ratio sion tivity is rropylene AN Bi-Mo-W-Ca 2:3:l:3 92.7 87.1

sobutylene MAN do. do. 93.1 86.3 60 Propylene AN do. 2:l:l:l 92.9 88.161 150- butylene MAN do. do. 93.9 85.8

washed and then dried at a temperatureof 120 to 130C for 16 hours.Successively, the dried coprecipitate was calcined at 540C for 16 hours,while blowing air. Thus, calcium molybdate [CaMoOfl was prepared. Thecalcium molybdate was identified by the results of the X-ray diffractiondiagram.

240 ml of a solution of 83.3 g tungstic acid [WO H O] dissolved in a9.3% aqueous ammonia (thus, the solution is an ammonium tungstatesolution having a concentration of 0.66 mol/l and 320 ml of a 485.1 gbismuth nitrate [Bi(NO );,.5H O] solution in a 13.8% nitric acid (theconcentration of bismuth nitrate: 1.0 mol/l were mixed with each otherwhile being stirred. The mixed solution was heated to dryness untilgeneration of ammonium nitrate and nitrogen oxide ceased. A small amountof water was added to the dried solid, followed by kneading for 2 hours.After drying at 120 to 130C for 16 hours, the dried solid was calcinedat 540C for 16 hours while blowing air. Thus, bismuth tungstate [Bi O-.WO was prepared. The bismuth tungstate was identified by the results ofthe X-ray diffraction diagram.

The calcium molybdate and the bismuth tungstate, so prepared, were mixedand kneaded together with a small amount of water for 3 hours. The pastewas dried at a temperature of 120 to 130C for 16 hours, and thencalcined at 540C for 16 hours while blowing air. The calcined solid wasdressed to grain of 14 to 20 EXAMT LES 62 69 BiMoWCa-Nb, Ti, V, Fe, Zror Ta catalyst By procedures similar to that of preparing bismuthtungstate in Example 58, bismuth niobate lBiNbO bismuth titanate [Bi TiO bismuth vanadate [BiVO bismuth ferrate [BiFeO bismuth zirconate [Bi(ZrO and bismuth tantalatelBiTaO were prepared wherein a solution ofbismuth nitrate in nitric acid; and niobium pentaoxide [Nb O titaniumdioxide [TiO a solution of ammonium metavanadate [NH VO in oxalic acid,an aqueous solution of ferric nitrate [Fe(NO .9H O], an aqueous solutionof zirconium nitrate [ZrO(NO .2H O] and tantalum pentaoxide [Ta O wereused, respectively. These six compounds were identified by the resultsof the X-ray diffraction diagrams.

From each of these six compounds and the calcium molybdate mentioned inExample 58 and the bismuth tungstate mentioned in Example 58, a catalystwas prepared in the same manner as that of Example 58.

Using the catalyst so prepared, ammoxidation reactions of propylene andisobutylene were performed by the same procedure as that of Example 58.The results are shown in Table V11.

EXAMPLES 70 and 71 Bi-Mo-W-Ca-Ti-Nb or Zr catalvst From the calciummolybdate in Example 58, the his muth tungstate in Example 58, thebismuth titanate in Example 65, the bismuth niobate in Example 62 andthe bismuth zirconate in Example 68, two catalysts were prepared in thesame manner as that of Example 5 Using the catalysts, ammoxidationreaction of propylene was performed by the same procedure as that ofExample 58. The results are shown in Table VII.

Table VII Exam- Conver- Selecple Feedstock Prod- Catalyst Atomic siontivity No. uct ratio /2) (71) 62 Propylene AN Bi-Mo-W 3:2:1:

Ca-Nb 2:1 93.2 88.8 63 lso butylene MAN do. do. 93.4 87.3 64 PropyleneAN do. 3:121:

1:] 93.0 89.3 65 do. do. Bi-Mo'W- 4:1:1:

Ca-Ti 1:2 92.9 89.4 66 do. do. Bi-Mo-W- 311:]:

1:] 93.1 86.9 Ca-V 67 do. do. Bi'Mo-W- 3:1:1:

Ca-Fe 1:] 93.1 90.7 68 do. do. Bi-Mo-W- 4:1:1:

Ca-Zr 1:3 93.3 90.4 69 do. do. Bi-Mo-W- 3:1:1:

Ca-Ta 1:1 92.9 87.1 70 do. do. Bi-Mo-W- 5: 1:1:

Ca-Ti-Nb 1:2:1 94.0 87.3 71 do. do. Bi-M0 W- 7:|:|:

Ca-Ti-Zr 1:2:3 94.1 86.6

EXAMPLES 72 77 Bi-MoW-CaCr-Ti catalyst 32.4 g of ammonium [(NH .,W O .5HO], 49.7 g of chromium nitrate [Cr(NO .9H O]. 9.9 g of titanium dioxide[TiO and 220.0 g of calcium nitrate [Ca(NO .4H O] were dissolved in 11of water maintained at 60C, while being 40 stirred. To this solution,were added by drops at the same time a solution of 150.6 g bismuthnitrate [Bi(- NO .5H O] in 181 ml ofa 10% nitric acid and a solu- 3paratungstate steam, a molar ratio of the four components being 27 5 27300 106 respectively, was passed through the Table VIII Exam- FeedstockProd- Catalyst Atomic Con- Selecple uct ratio ver tivity No. sion (72)72 Propylene AN Bi-Mo-W-Ca- 1:2.0:

Cr-Ti 04:3: 95 3 87.1

04:04 73 Isobutylene MAN do. do. 95.7 87.1 74 Propylene AN do. l:2:0.2:

3:04:04 92.8 85.3 75 do. do. do. 1:2:0.4:

3:0.8:0.4 91.5 86.8 76 do. do. do. 1 1.5108

:3:0.2: 95.2 84.4 0,4 77 do. do. do. 1:12:02:

tron of 109.7 g ammonium molybdate In order to evaluate the dlmensionalstability and the [(NH. ;Mo O .4H O] in 260 ml ofa 10% aqueous ammonia.lrnmediately thereafter, a 10% aqueous ammo nia was added to the mixedsolution thereby adjusting the pH to 4.0 to form a precipitate. Afterleaving overnight the precipitate was washed by repeatingdecantamechanical properties of the catalysts employed, crushingstrength and diameter of the tabletted catalysts were determined. Thedetermination was made on specimen catalysts before and after it wasused in the conversion of olefin to nitrile under the followingprocedure. That is, 10 ml of a specimen catalyst having 5 mm diameterand approximately 5 mm height was packed into a U-shaped glass reactiontube. A gaseous mixture of propylene, ammonia, air and steam, a molarratio of the four components being 10 l 100 10, was passed through thecatalyst packed reaction tube maintained at 500C at a flow rate of 130ml/min over a period of 200 hours. The measurement of both crushingstrength and the diameter was made on the approximately 50 tablettedspecimen catalysts, and average values were calculated. In thedetermination of crushing strength, a KlYA type hardness tester wasemployed.

Test results are shown in Table 1X.

conditions remaining the same. The results are shown in Tables X and X1.

EXAMPLES 80 83 48.0 g of ammonium paratungstate [(NHQ W O SH OJ, 28.8 gof chromium nitrate [Cr(NO .9H O], 9.4 g of niobium pentaoxide lNb O and251.3 g of calcium nitrate [Ca(NO .4- H O] were dissolved in 1 l ofwater maintained at 60C while being stirred. To this solution, wereadded by drops at the same time a solution of 172.2 g bismuth nitrate[Bi(NO .5I-l O] in 207 ml of a nitric acid and a solution of 125.5 gammonium molybdate [(NH Mo O .4H O] in 298 m1 ofa 10% aqueous ammonia.Immediately thereafter, a 10% aqueous ammonia was added the mixedsolution thereby adjusting the pH to 4.0 to form a precipitate. Theprecipitate was treated in the same manner as that of Example 72 toprepare a tabletted catalyst.

Using the catalyst so prepared, ammoxidation reaction of propylene wasperformed by the procedure of Example 72.

In Examples 81, 82 and 83, the above procedure was followed whereincatalysts containing the six metal ingredients at varied atomic ratioswere employed with all other conditions remaining substantially thesame. The results are shown in Tables X and X1.

'TZEIEX Exam- Conver- Selecple Feedstock Prod- Catalyst Atomic siontivity No. uct v ratio (7r) 78 Propylene AN Bi-Mo-W- 1:2:0.8:3:

Ca-Cr-Zr 022:0.2 79 do. do. do. 12210.5:3:

0520.5 97.2 86.1 80 do. do. Bi-Mo-W- l.2:0.5:3:

Ca-Cr-Nb 0.2:0.2 95.7 85.7 81 do. do. do. l:2:O.8:3:

O.2:0.6 93.2 86.3 82 do. do. do. l:l.5:0.2:

2:0.8:0.4 92.8 87.2 83 do. do. do. 1.1:0.4:6:

EXAMPLES 78 and 79 5 Table XI BiMoWCaCr-Zr catalyst 75.1 g of ammoniumparatungstate E p g Strength Diameter uNHnmwlzofl'sHzol g of Chromiumnitrate 0 Before use After use Before usi hfter use [Cr(NO .9H O], 19.0g of zirconium nitrate [ZrO(- nomzn o and 254.8 g of calcium nitrate[Ca(- 78 17.0 4B0 NO .4H O] were dissolved in l l of water maintained g8:21; lg? 21;? L18 at C while being stirred. To this solution, were 8113.2 13.6 4.76 4.75 added by drops at the same time a solution of 174.5g 3% 12'? :26 2'3; 2 bismuth nitrate [Bi(NO -,.5H O] in 210 ml ()ffl 10%5s nitric acid and a solution of 127.2 g ammonium molybdate [(NH. ).,MoO .4H- ,O] in 302 ml ofa 10% aqeuous ammonia. Immediately thereafter, a10% aqueous ammonia was added to the mixed solution thereby adjustingthe pH to 4.0 to form a precipitate. The precipitate was treated in thesame manner as that of Example 72 to prepare a tabletted catalyst.

Using the catalyst so prepared, ammoxidation reaction of propylene wasperformed by the procedure of Example 72.

in Example 79. the above procedure was followed wherein a catalystcontaining the six metal ingredients at a varied atomic ratio wasemployed with all other wherein I1 is at least one metal selected fromthe group consisting of calcium, barium and zinc; X isa single metalselected from the group consisting of titanium. zirconium. niobium,tantalum. vanadiunL chromium. manganese. iron. cobalt and nickel or atwo metal combination selected from the group consisting of titanium andniobium, titanium and zirco'nium chromium and titanium, chromium andzirconium and chromium and niobium; and each of the subscripts a, b. cand d denote the atomic ratio of the respective metal to bismuth andfalling within the following ranges a 03 to 10, b 0.05 to 3.0, c 0.1 to6.0 and :1 to 5.0, and e is a value corresponding to the oxides formedfrom the above components by combination and is a number which satisfiesthe average valency of the metals employed, and falls within the rangeof 3.2 and 61.5, said catalyst being a mixture of the metal oxides or inbonded state and being produced by intimately mixing at least onecompound selected from the group consisting of the salts, the oxides,and mixtures thereof of each of respective elements in an aqueoussystem. heating to dryness and then subsequently calcining at aconsiderably higher temperature.

2. A process as claimed in claim 1 wherein said mixture has a molarratio of ammonia to propylene or isobutylene in the range of 0.5 l to 3l and a molar ratio of oxygen to propylene or isobutylene in the rangeof 0.8 l to 4 l.

3. A process as claimed in claim 1, wherein said mixture furthercontains at least 0.5 mole of steam per mole of propylene orisobutylene.

4. A process as claimed in claim 1 wherein said mixture is contactedwith said catalyst at a temperature of 300 to 550C.

5. A process as claimed in claim 1, wherein said mixture is contactedwith said catalyst for a period of 0.3

1. A PROCESS FOR THE MANUFACTURE OF ACRYLONITRILE OR METHACRYLONTRILE FROM PROPYLENE OR ISOBUTYLENE, RESPECTIVELY, COMPRISING CONTACTING IN THE VAPOR PHASE AT AN ELEVATED TEMPERATURE A MIXTURE OF PROPYLENE OR ISOBUTYLENE, AMMONIA AND OXYGEN WITH A CATALYST CONSISTING OF AN OXIDE COMPOSITION CONTAINING THE ELEMENTS ACCORDING TO THE FORMULA
 2. A process as claimed in claim 1 wherein said mixture has a molar ratio of ammonia to propylene or isobutylene in the range of 0.5 : 1 to 3 : 1 and a molar ratio of oxygen to propylene or isobutylene in the range of 0.8 : 1 to 4 :
 1. 3. A process as claimed in claim 1, wherein said mixture further contains at least 0.5 mole of steam per mole of propylene or isobutylene.
 4. A process as claimed in claim 1 wherein said mixture is contacted with said catalyst at a temperature of 300* to 550*C.
 5. A process as claimed in claim 1, wherein said mixture is contacted with said catalyst for a period of 0.3 to 20 seconds. 